CN87106917A - Novel halogenated cyclopropyl compound, its preparation method and as herbicide applications - Google Patents

Novel halogenated cyclopropyl compound, its preparation method and as herbicide applications Download PDF

Info

Publication number
CN87106917A
CN87106917A CN198787106917A CN87106917A CN87106917A CN 87106917 A CN87106917 A CN 87106917A CN 198787106917 A CN198787106917 A CN 198787106917A CN 87106917 A CN87106917 A CN 87106917A CN 87106917 A CN87106917 A CN 87106917A
Authority
CN
China
Prior art keywords
compound
formula
cotype
definition
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN198787106917A
Other languages
Chinese (zh)
Inventor
弗里德海姆·布鲁姆
威尔夫里德·弗朗克
弗里德里克·阿恩特
里查德·里斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Pharma AG
Original Assignee
Schering AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schering AG filed Critical Schering AG
Publication of CN87106917A publication Critical patent/CN87106917A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Indole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The present invention open novel halogenated cyclopropyl compound of formula I, wherein R 1, R 2, R 3, X, Y, n, U, V and W be as described in the specification sheets.

Description

Novel halogenated cyclopropyl compound, its preparation method and as herbicide applications
The present invention relates to novel fontanel for cyclopropyl compounds, the preparation method who presses currently known methods with and as herbicide applications.
Known some tetrahydrochysene indazole and tetrahydric phthalimide have weeding characteristic (EP61741 and 105721).Before these material buds behind the bud application of active all fine but its shortcoming is and some crop such as cotton that the consistency of soybean and cereal is not enough.
Find unexpectedly that now formula I fontanel is for cyclopropyl compounds and paddy rice, wheat, soybean, corn, the consistency of cotton and barley is fine, has significant weeding activity simultaneously again.
Figure 87106917_IMG28
Wherein
R 1, R 2And R 3Be respectively hydrogen or 1-4 carbon alkyl,
X is hydrogen or fontanel element,
Y is the fontanel element,
N is 0,1,2 or 3
U and V be hydrogen or fontanel element and
W is following heterocyclic radical
Figure 87106917_IMG29
Wherein
T is the fontanel element, 1-4 carbon alkyl, 1-4 carbon fontanel substituted alkyl, CN or OR 9,
Q is CH or N,
Z is O or S,
R 4, R 5, R 6, R 7And R 8Be respectively straight chain, branching or ring-type 1-7 carbon alkyl also can be replaced by 1-6 fontanelle atom in case of necessity, or
R 4And R 5Also can form saturated together or unsaturation 4-7 annulus, wherein can contain heteroatomss such as O, S or N, in case of necessity also can by 1-3 methyl or 1-6 fontanelle atom replace and
R 9Be hydrogen, 1-4 carbon alkyl or 1-4 carbon fontanel substituted alkyl.
" fontanel element " is F, Cl, and Br or I, existing one or more hydrogen atom has been replaced by the fontanel element in the alkyl and " fontanel substituted alkyl " means.
The heterocycle object lesson comprises: the pyrroles, oxazole, thiazole, imidazoles, pyridine, oxazine, thiazine, pyrimidine, pyrazine, triazine, oxadiazine and thiadiazine with and two, four or be preferably six hydroperoxide derivatives.
The compounds of this invention can make according to following proposal by known way:
A) with formula II fontanelle compound and the reaction of formula III phenol
R wherein 1, R 2, R 3X, Y and the definition of n cotype I, A is Cl, Br or L,
Figure 87106917_IMG31
U wherein, V and the definition of W cotype I,
Or
B) be 4,5,6 for making W, the formula I compound of 7-tetrahydrochysene indazole-2-base is with formula IV compound and the reaction of formula V compound
Figure 87106917_IMG32
R wherein 1, R 2, R 3X, Y, n, U, the definition of V cotype I,
Figure 87106917_IMG33
R wherein 10Be 1-4 carbon alkyl, 1-4 carbon fontanel substituted alkyl or 1-4 carbon alkoxyl group,
The formula I that can be hydroxyl in case of necessity with the T that makes like this is compound modified as reacting to such an extent that T is the corresponding compound of alkoxyl group or reacts to such an extent that T is that the corresponding compound of fontanel element and also available in case of necessity Na CN processing change into the corresponding compound that T is CN with phosphoryl chloride with the sulfuric acid dialkyl
Or
C) be 2H-1 for making W, 2, the formula I compound of 4-triazoline-3-ketone-2-base is with above-mentioned formula IV compound and the reaction of formula VI compound
R wherein 4And R 5The definition of cotype I, R 11Be 1-4 carbon alkyl,
Or
With above-mentioned IV compound of formula and the reaction of formula XII ketone acid
Figure 87106917_IMG35
R wherein 8The definition of cotype I,
Thereby make formula XI compound
Figure 87106917_IMG36
R wherein 1, R 2, R 3, R 8, X, Y, n, U and the definition of V cotype I are carried out the cyclisation processing and are made formula XX III compound with the phosphoric acid ester trinitride again
R wherein 1, R 2, R 3, R 5, X, Y, n, U and the definition of V cotype I can also be reacted itself and formula X compound in case of necessity
R wherein 4The definition of cotype I, A is Cl, Br or I,
Or
D) be 3H-1 for making W, 3, the formula I compound of 4-diazole-2-ketone-3-base is with above-mentioned formula IV compound and the reaction of formula VIII acid derivative
Figure 87106917_IMG38
R wherein 6The definition of cotype I, R 12Be fontanel element or 1-4 carbon alkoxyl group, thereby make formula VII intermediate product
Figure 87106917_IMG39
R wherein 1, R 2, R 3, R 6, X, Y, n, U and the definition of V cotype I,
Again with the derivatives reaction of itself and phosgene or its band active function groups,
Or
E) be 2H for making W, 4H-1,2,4-triazine-3, the formula I compound of 5-diketone-2-base is with above-mentioned formula IV compound and the reaction of formula XII ketone acid
Figure 87106917_IMG40
R wherein 8The definition of cotype I,
Thereby make formula XI compound
Figure 87106917_IMG41
R wherein 1, R 2, R 3, R 8, X, Y, n, the definition of U and V cotype I, then with it with thionyl (two) chlorine or phosphoryl chloride and carrying out cyclisation and making formula IX compound with carbamate thereafter
Figure 87106917_IMG42
R wherein 1, R 2, R 3, R 8, X, Y, n, U and the definition of V cotype I are reacted itself and formula X compound again
R wherein 7The definition of cotype I, A is Cl, Br or I,
Or
F) be 4,5,6 for making W, 7-tetrahydrochysene-2H-1,2, the formula I compound of 3-triazolo [3,4-a] pyridine-8--3-olation-2-base is used the diacetyl oxide cyclisation with formula X V compound after with nitrous acid diazotization with piperidines-2-carboxylic acid reaction and thereafter
Figure 87106917_IMG43
R wherein 1, R 2, R 3, X, Y, n, U and the definition of V cotype I,
G) be 1,3,4,5,6 for making W, 7-six hydrogen-2H-isoindole-1, the formula I compound of 3-diketone-2-base is with above-mentioned formula X V and the reaction of formula X VI
Wherein Z is O or S,
Or
H) be 2,3,5,6,7 for making W, 8-six hydrogen-1H-imidazo [1,5-a]-pyridine-1,3-diketone-2-base or 2,3,5,6,7,8-six hydrogen-1H-1,3,4-triazolo [1,2-a]-pyridazine-1, the formula I compound of 3-diketone-2-base is with above-mentioned formula X V compound and formula X VII or the reaction of X VIII compound
Figure 87106917_IMG45
Wherein Z is O or S, and Q is CH or N, R 15Be 1-4 carbon alkyl,
Or
Above-mentioned formula X V compound and phosgene or thiophosgene reaction can be made formula X IX compound,
R wherein 1, R 2, R 3, X, Y, n, U, V and the definition of Z cotype I,
And then with formula X IX compound and the reaction of formula XX compound
Wherein Q is CH or N, and Z is O or S, R 15Be 1-4 carbon alkyl,
Or
I) formula XX I compound and formula XX II fontanel are reacted for methane Derivatives
Figure 87106917_IMG48
R wherein 1, R 2, R 3, U, V, W and the definition of n cotype I,
Figure 87106917_IMG49
Wherein X and Y cotype I the definition, B be hydrogen or
Figure 87106917_IMG50
, wherein M is a basic metal.
According to the preparation scheme a), reaction can be suitably by acid acceptor in 0-150 ℃ particularly room temperature to the reaction mixture refluxed temperature, carry out.The appropriate acid receptor comprises common alkali particularly aliphatic amide such as triethylamine or Diisopropylamine and alkaline carbonate and aqueous solution thereof or the like.
Etherification reaction also useful catalyst carries out in solvent in biphasic system and in case of necessity.Suitable alkali comprises solid-state or water-soluble liquid alkali metal hydroxide and carbonate or the like.Suitable solvent comprises reactant itself (as for liquid) or the like.In addition, availablely do not mix and alkali is become inert material such as fat or aromatic hydrocarbon such as hexane, benzene or toluene or the like with water.Preferred catalyst be crown ether as 1,4,7,10,13,16-six oxygen ring octadecanes and quaternary ammonium salt (see Dehmlow and Dehmlow, Phase Transfer Catalysts, Weinhem 1980) or the like.
The stoichiometrical starting material of general employing, but also can make certain starting material excessive under some situation.
According to the preparation scheme b) and c), reaction is generally carried out in the presence of catalyzer in suitable solvent.Temperature of reaction is generally ℃ particularly reflux temperature of reaction mixture of room temperature-150.Suitable solvent comprises methyl-sulphoxide, and fontanel is for hydrocarbon such as methylene dichloride and chloroform, aromatic hydrocarbons such as benzene, and toluene, dimethylbenzene, chlorobenzene becomes inert solvent such as ether with dichlorobenzene and other to reactant, and tetrahydrofuran (THF) becomes dimethyl formamide or the like.
The catalyzer object lesson comprises that acid is as acetate or sulfuric acid and acidic ion exchange resin.
According to the preparation scheme d), reaction is generally carried out being with or without under the suitable inert solvent.Suitable solvent comprises methyl-sulphoxide, and fontanel is for hydrocarbon such as methylene dichloride and chloroform, aromatic hydrocarbons such as benzene, and toluene, dimethylbenzene, chlorobenzene becomes inert solvent such as ether to reactant, tetrahydrofuran (THF) or dimethyl formamide or the like with dichlorobenzene and other.
According to preparation method e), the reaction of formula IX compound and formula X compound can be suitably by acid acceptor in 0-150 ℃ particularly room temperature to the reaction mixture refluxed temperature, carry out.Appropriate acid accepts to comprise common alkali particularly aliphatic amide such as triethylamine or Diisopropylamine and alkaline carbonate and aqueous solution thereof or the like.
The alkylated reaction useful catalyst is carried out in solvent in biphasic system and in case of necessity.Suitable alkali comprises solid-state or water-soluble liquid alkali metal hydroxide and carbonate or the like.Suitable solvent comprises reactant itself (as for liquid) or the like.In addition, availablely do not mix and alkali is become inert material such as fat or aromatic hydrocarbon such as hexane, benzene or toluene or the like with water.Suitable catalyzer comprises crown ether and quaternary ammonium salt or the like.
General adopt stoichiometric starting material, but also can make certain or some starting material excessive under some situation.
According to preparation scheme f), reaction is generally carried out and the intermediate product of not purifying therebetween in three stages.Dewater and also available outward any inert organic solvents.Temperature of reaction is-20-100 is ℃ particularly-10 ℃ to room temperature.
According to preparation scheme g) and h), reaction is generally carried out under the reflux temperature of the temperature more than 20 ℃ as 100 ℃ or reaction mixture.When one of reactant is an acid anhydrides during suc as formula X VI or X VII compound, reaction can suitably be carried out as in the presence of the acetate in acid, and wherein acetate can be used as solvent again.But reaction also can be crossed and carry out also available acid anhydrides such as diacetyl oxide in the presence of the methyl-sulphoxide with the cyclisation of interstitial chiasma product being with or without inert solvent such as methylene dichloride.
According to the preparation scheme h that carries out with formula X IX and XX compound), reaction is generally particularly carried out under the solvent boiling point in 20-150 ℃ in inert solvent.But suitable solvent comprises chlorating aliphatic and aromatic hydrocarbons such as sherwood oil in case of necessity, benzene, toluene, dimethylbenzene, methylene dichloride, chloroform, tetrachloromethane, 1,2-ethylene dichloride and chlorobenzene and ether such as ether and n-butyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF) is with diox, ketone such as acetone, methylethylketone and methyl isopropyl Ketone and nitrile such as acetonitrile and propionitrile and sulfoxide such as methyl-sulphoxide or tetramethylene sulfone or the like.
According to preparation scheme i), reaction is generally becoming inert solvent such as chloroform to reactant, ether such as dioxane or diethylene glycol dialkyl ether, in aliphatic hydrocarbon such as hexanaphthene or the decane in room temperature to 200 ℃ particularly under solvent boiling point and where necessary also by the influence of highly basic such as alkali metal alcoholate or oxyhydroxide and preferably adopt phase reforming catalyst such as Dehmlow and Dehmlow to carry out at catalyzer described in " Phase Transfer Catalysts, Weinhem 1980 " with biphasic system.
The The compounds of this invention that makes according to the method described above can in a usual manner as adopt normal pressure or underpressure distillation solvent or extraction process to separate.
Generally also can adopt column chromatography and fractionating process to improve purity.
The compounds of this invention generally becomes crystal or viscous substance, and a part, is very easily dissolved in sulfoxide such as methyl-sulphoxide or ester such as the ethyl acetate for hydrocarbon such as chloroform at fontanel.
The compounds of this invention also can contain one or more asymmetric c atoms.The present invention also comprises optically active form in case of necessity and composition thereof.In an embodiment.And outer, what obtain is racemoid unless otherwise indicated.
Formula IV and X V initial substance can make by currently known methods, and feasible route of synthesis is shown in following reaction process:
Figure 87106917_IMG51
The preparation of other starting material is just no longer explanation here, because these starting materials are knownly maybe can to make by the similarity method of currently known methods.
The compounds of this invention has significant weeding activity to of great weight unifacial leaf of cash crop and broadleaf weed, and prior to seeding, sprays before the bud or behind the bud and all can.
Also find The compounds of this invention and paddy rice unexpectedly, wheat, soybean, corn, the consistency of cotton and barley is fine.
The compounds of this invention can be used for removing following weeds:
Following broadleaf weed: Tong fiber crops belong to Chrysanthemum, Btassica, Helianthus, Mentha, mustard belongs to, separate row Vegetable spp, Bedstraw, stellera, Anthemis, Chenopodium, atriplex, Senecio, Portulaca, Ipomoea, Matricaria, ox achyranthes chrysanthemum spp, Urtica, Amaranthus, Polygonum, Daubentonia, Ambrosia, sonchus L, Solanum, lamium, Veronica, Datura, Viola, bachelor's-button and weasel hemp nettle belong to;
Following monocotyledon weed: Avena, amur foxtail belongs to, Echinochloa, dog hair grass belongs to, Panicum, knotgrass, annual bluegrass belongs to, yard grass belongs to, Brachiaria, and lolium temulentum belongs to, Brome, the lotus grass belongs to Agropyron, arrowhead belongs to, bermudagrasses, Monochoria, genus fimbristylis, Eleocharis, lschaemum and Apera.
The compounds of this invention is not limited in above-mentioned weeds and crop, but can be used for other plant similarly.
The present invention also be suitable for big consumption be used for to around the factory and railway along the line and the weeds on road both sides and the vacant lot carry out overhead control, also can be used to remove long-term cultivation area such as forest, amenity, the orchard, vineyard, citrus garden, the nut garden, banana garden, coffee garden, tea plantation, the rubber plantation, the oil palm garden, palm grove, the weeds in oar orchard and the hops garden.
The active substance consumption can change in wide range, mainly decides on the effect that need reach, and general consumption is 0.01-5kg active substance/ha, and the weeding preferable amount is 0.1-0.5kg active substance/ha.
As want to enlarge activity profile, also can use other weedicide with.The mix weeding active ingredient that this respect is suitable for comprises Wees Abstracts, Vol.35, No.3, in 1986 with active weedicide listed in the article that is entitled as " Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts " or the like.
Said active substance or its mixture can be suitably with wettable powders, dusting, grain, solution, dosage forms such as emulsion or suspension are applied, and wherein add liquid state and/or solid-state carrier and/or thinner and also add tackiness agent in case of necessity, wetting agent, emulsifying agent and/or dispersion agent.
Suitable liquid vehicle comprises aliphatic and aromatic hydrocarbons such as toluene, dimethylbenzene and pimelinketone, isophorone, methyl-sulphoxide, dimethyl formamide and other mineral oil component and vegetables oil or the like.
Suitable solid carrier comprises mineralogical composition such as gypsum, Tonsil, wilkinite, silica gel, talcum, kaolin, attapulgite, Wingdale, silicic acid and plant prod such as flour or the like.
Tensio-active agent can be used calcium lignosulfonate, the polyethylene alkyl phenyl ether, polyethylene oxide-sorbitol ester, polyethylene oxide-poly(propylene oxide) superpolymer, naphthene sulfonic acid and salt thereof, the cats product of the tertiary amine that band portion can be replaced by polyethoxye, sulfocarbolic acid and salt thereof, formaldehyde condensation products, aliphatic alcohol sulfate and substituted benzenesulfonic acid and salt thereof.
Activeconstituents per-cent can change in very wide scope as wherein containing about 10-90%w/w activeconstituents and about 90-10%w/w liquid state or solid-state carrier and can containing up to 20%w/w tensio-active agent in case of necessity in the various preparations.
Preparation can be used according to a conventional method as using water as the consumption spray formulation mixture of carrier with about 100-3000 l/ha v/v, also can adopt so-called low volume or ultralow volume technology to use with so-called particulate form.
These preparations can adopt ordinary method to make as grinding or hybrid technique.Also can shortly before using, just each composition be mixed as adopting so-called day tank mixing method to mix in case of necessity.
Give an example as the present invention, adopt following ingredients to make following preparation (content is by weight):
A1) wettable powder
80% active substance
10% kaolin
2%N-methyl-N-oleoyl Sodium taurine salt
8% calcium lignosulfonate
A2) wettable powder
20% active substance
35% wilkinite
8% calcium lignosulfonate
2%N-methyl-N-oleoyl Sodium taurine salt
35% silicic acid
B) stick with paste
45% active substance
5% lagoriolite
Mixing of 15% hexadecyl polyglycol ether and 8 moles of ethylene oxide gathers product
2% spindle oil
10% polyoxyethylene glycol
23% water
C) missible oil
20% active substance
75% isophorone
2% 12 (alkane) basic Phenylsulfonic acid calcium
3% fatty alcohol polyglycol ether
Following is the The compounds of this invention preparation example.
Preparation example 1
N-[4-chloro-5-(2,2-dichloro cyclo propyl methoxy)-the 2-fluorophenyl]-3,4,5,6-tetrahydric phthalimide (compound N is o.1.1)
With 8.9g(0.031mol) 4-chloro-2-fluoro-5-(2,2-dichloro cyclo propyl methoxy) aniline is dissolved in 12.5ml acetate and adds 3.85g 3,4,5, the 6-Tetra Hydro Phthalic Anhydride.The mixture reflux is poured into after 3 hours and is used extracted with diethyl ether in the frozen water.Ether washs the back with dried over mgso and except that desolvating with the sodium bicarbonate aqueous solution neutralization with saturated brine.Resistates carries out the silica gel chromatography analysis with the mixture that 9 parts of hexanes add 1 part of ethyl acetate as elutriant.
Obtain brown crystal 7.8 grams (75% of theoretical value, m.p.121-122 ℃).
Can make following compound with similar approach:
Figure 87106917_IMG52
Compound R 1R 2R 3N X Y U V physical constant
No
1.2????H????H????H????1????F????F????Cl????F????n＝1.5375
1.3????H????H????H????2????F????F????Cl????F????n＝1.5280
1.4????H????H????H????2????Cl????Cl????Cl????F????n＝1.5555
Preparation example 2
2-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-and the 2-fluorophenyl]-4,5,6,7-tetrahydrochysene-(2H)-1,2,3-triazoles is [3,4-a] pyridine-8--3-ol bridge compound (compound N is o.2.1) also
With 4.6g 4-chloro-5-(2,2-dichloro cyclo propyl methoxy)-the 2-fluoroaniline is dissolved in the mixture of 9.7ml concentrated hydrochloric acid and 41.5ml water and with mixture and is chilled to-10 ℃.Be added dropwise to the 4.2ml aqueous solution of 1.38g Sodium Nitrite then, its interpolation speed should make the temperature of reaction mixture be unlikely and rise to more than-5 ℃.Consume excessive nitrous acid afterwards again in-5 ℃ of stirrings 1 hour and with urea till iodine examination starch paper is tested into negativity.Gained solution is heated to and is added dropwise to after 0 ℃ in 2.3g pipecolic acid and the ice-cooled solution of 8.3ml triethylamine in 27.7ml water.Stir 1 hour also several times in 0 ℃ more afterwards with the dichloromethane extraction reaction mixture.Combine organic phase with dried over mgso and steam solvent.Resistates extracts in the 40ml ether and adds the 4.14ml diacetyl oxide and the 2.07ml pyridine is handled.Pour in the frozen water after mixture stirs under room temperature and spends the night and use ethyl acetate extraction.Organic phase is with dried over mgso and steam solvent.Resistates adds 5 parts of methanol mixture with 95 parts of ethyl acetate and carries out the silica gel chromatography analysis as elutriant.
Obtain crystal 0.9 gram (13.4% of theoretical value, m.p.125-127 ℃).
Preparation example 3
3-chloro-2-[4-chloro-5-(2,2-difluoro cyclopropyl oxyethyl group)-the 2-fluorophenyl]-4,5,6,7-tetrahydrochysene-2H-indazole (compound N is o.3.1)
With 5g4-chloro-5-(2,2-difluoro cyclopropyl oxyethyl group)-2-fluorophenyl hydrazine is dissolved in the 18ml acetate, adds 2.85ml pimelinketone-2-carboxylic acid, ethyl ester again and with mixture reflux 8 hours.Then mixture is poured into and used dichloromethane extraction in the water.Organic phase is with the potassium bicarbonate aqueous solution neutralization and with using dried over mgso after the saturated brine washing.Steam solvent get the 8.4g(theoretical value 100%) crude product.After this product is handled with the 3.6ml phosphoryl chloride with the mixture reflux.After 4 hours with its cooling and in methylene dichloride, extract, water and thereafter with saturated soda solution washing back with dried over mgso and steam solvent, resistates adds 5 parts of methanol mixture with 95 parts of methylene dichloride and carries out the silica gel chromatography analysis as elutriant.
Obtain 35.6% of brown oil 2.6g(theoretical value, n 25 D=1.5345).
Figure 87106917_IMG53
Compound R 1R 2R 3N X Y U V physical constant
No
3.2????H????H????H????1????F????F????Cl????F????n＝1.538
3.3????H????H????H????1????Cl????Cl????Cl????F????n＝1.5713
3.4????H????H????H????2????Cl????Cl????Cl????F????n＝1.5615
Preparation example 4
2-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-the 2-fluorophenyl]-2,3,5,6,7,8-six hydrogen-1,2,4-triazolo [4,3-a] pyridine-3-ketone (compound N is o.4.1)
With 3g4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-2-fluorophenyl hydrazine is dissolved in the 40ml dimethylbenzene and adds 2.4g 1-ethoxy carbonyl-2-piperidone and 1g Vanadium Pentoxide in FLAKES.The mixture reflux is poured in the 100ml water and is isolated organic phase after 3 hours.This organic phase is also removed with dried over mgso with in the potassium bicarbonate aqueous solution and back and is desolvated.Resistates first and second acetoacetic esters carry out the silica gel chromatography analysis as elutriant.
Obtain 23% of oily matter 1.2g(theoretical value, n 20 D=1.5438).
Figure 87106917_IMG54
Compound R 1R 2R 3N X Y U V physical constant
No
4.2????H????H????H????1????Cl????Cl????Cl????F????n＝1.5655
4.3????H????H????H????2????Cl????Cl????Cl????F????n＝1.5620
4.4????H????H????H????2????F????F????Cl????F????n＝1.5332
Preparation example 5
2-[4-chloro-5-(2,2-difluoro cyclopropyl oxyethyl group)-the 2-fluorophenyl]-3-sulfo--2,3,5,6,7,8-six hydrogen-1H-imidazo [1,5-a] pyridine-1-ketone (compound N is o.5.1)
With 2.9g4-chloro-5-(2,2-difluoro cyclopropyl oxyethyl group)-2-fluorophenyl lsothiocyanates is dissolved in the 20ml hexane and mixture is added dropwise to the 10ml hexane solution of 1.5ml piperidines-2-carboxylic acid, ethyl ester.Mixture reflux 2 hours.Remove the back resistates that desolvates and carry out the silica gel chromatography analysis as elutriant with the mixture that 3 parts of hexanes add 1 part of ethyl acetate.
Obtain 82% of viscosity oily matter 3.2g(theoretical value, n 40 D=1.54).
Preparation example 6
2-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-the 2-fluorophenyl]-2,3,5,6,7,8-six hydrogen-1H-imidazo [1,5-a] pyridine-1,3-diketone (compound N is o.6.1)
With the method that is similar to preparation example 5 with 8.33g4-chloro-2-fluoro-5-(2,2-difluoro cyclo propyl methoxy) phenyl lsothiocyanates and 4.69ml piperidines-2-carboxylic acid, ethyl ester in the 100ml hexane, react can obtain semi-crystalline oily product 7.7g(theoretical value 6%), its NMR spectrum is as follows:
δ＝1，1-2，4ppm（m）9H，δ＝2.7-3.15ppm（m）1H，
δ＝3.85-4.4ppm（m）4H，δ＝6.87（d????6Hz）1H，
δ＝7.3（d????9Hz）1H
Preparation example 7
3-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-the 2-fluorophenyl]-the 5-tertiary butyl-1,3,4-oxadiazole quinoline-2-(3H)-ketone (compound N is o.7.1)
With 3g4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-and 2-fluorophenyl hydrazine hydrochloride is suspended in the 18.5ml toluene, and handle and mixture is stirred to the hydrochloride dissolving with the 3.6ml triethylamine.Slowly add the 1.6ml pivalyl chloride then without cooling and mixture was stirred under room temperature 2 hours.The reaction mixture water is used the saturated potassium hydrogen carbonate aqueous solution then, washes with water more afterwards, after this with dried over mgso and except that desolvating.The removal of impurity in the red oily product of the 3.7g that obtains as resistates and contain N '-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-2-fluorophenyl] pivaloyl hydrazide outward.This crude product is dissolved in the toluene solution of 22ml 20% phosgene, slowly be heated to 100 ℃ after insulation 3 hours.Concentrate after handling with its cooling and with 20ml methyl alcohol then.Resistates extracts in methylene dichloride, washes twice and wash with water once the back with dried over mgso and concentrate with saleratus.The gained crude product carries out the silica gel chromatography analysis to purify with hexane/ethyl acetate mixture (4: 1) as elutriant.
Obtain 24.5% of product 1.2g(theoretical value, n 20 D=1.5082).
Preparation example 8
N-[4-chloro-5-(2,2-difluoro cyclopropyl propoxy-)-the 2-fluorophenyl]-5,6,7,8-tetrahydric phthalimide (compound N is o.8.1)
With 1.2g N-[4-chloro-2-fluoro-5-vinyl oxygen phenyl)-5,6,7, the 8-tetrahydric phthalimide is dissolved in the 5ml diethylene glycol dimethyl ether, slowly adds the 20ml diethylene glycol dimethyl ether solution of 2.8g chlorine difluoroacetic acid sodium after mixture heating up refluxes.Again the mixture reflux is separated from the sodium-chlor that generates after 5 hours and removed and desolvate.Resistates carries out the silica gel chromatography analysis with hexane/ether mixture (1: 1) as elutriant.
Obtain 43% of crystalline substance 0.6g(theoretical value, m.p.105-107 ℃).
Preparation example 9
1-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-the 2-fluorophenyl]-4-difluoromethyl-3-methyl isophthalic acid, 2, the 4-bisoxazoline-5-(4H)-ketone (compound N is o.9.1)
With 8.2g4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-2-fluorophenyl hydrazine hydrochloride is dissolved in the 163ml water, splashes into the 81ml aqueous solution of 2.75ml pyruvic acid earlier afterwards again with the 81ml Ethanol Treatment.Mixture stirs after 1 hour and leaches precipitated product and carry out drying.Obtain still some impure hydrazone 7.9g, can be applied like this.
Hydrazone is dissolved in the 130ml toluene, gets limpid until solution becomes with processing of 3.3ml triethylamine and heating.It is cooled to about 35 ℃ and be added dropwise to di(2-ethylhexyl)phosphate phenylester trinitride, again mixture slowly is heated to 75 ℃.Be incubated under this temperature till no nitrogen generates, then reflux.With its cooling, with 10% caustic soda soln washing 3 times, water is used twice of toluene wash and in addition acidifying again after 12 hours.Product with after the toluene extraction with the organic phase drying.Remove the after product that desolvates and carry out the silica gel chromatography analysis as elutriant with ethyl acetate.Obtain 1-[4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-the 2-fluorophenyl]-the 3-methyl isophthalic acid, 2,4-triazoline-5-(4H)-ketone 3.7g(theoretical value 35%).
Above-mentioned products therefrom is dissolved in the 300ml hexanaphthene, handles, feed chlorodifluoromethane after mixture heating up is refluxed with 2.7g potassium hydroxide and 2g bromination four butylamine.React completely and solution is inclined to after (being illustrated by thin-layer chromatography), each is with 1N hydrochloric acid and 10% caustic-soda aqueous solution washed twice, with concentrating after the dried over mgso.Resistates is with ethyl acetate and carrying out the silica gel chromatography analysis with methylene dichloride as elutriant thereafter.
Obtain 2% of product 80mg(theoretical value, n 40 D=1.535).
Prepare some starting material
Preparation 4-chloro-5-(2,2-difluoro cyclo propyl methoxy)-the 2-fluoronitrobenzene
3.6 2-chloro-4-fluoro-5-nitrophenol are dissolved in the dimethyl formamide and with salt of wormwood handle.Mixture stirred under room temperature 1 hour, added 3.3g 2 then, 2-difluoro cyclopropyl monobromomethane.During heating was fallen back in 2 hours under 80 ℃ with it.Mixture with dichloromethane extraction after organic phase wash with saturated brine, with dried over mgso and concentrate.Resistates carries out the silica gel chromatography analysis with the mixture that 3 parts of hexanes add 1 part of ethyl acetate as elutriant.Obtain yellow crystals 5g(theoretical value 93%), its NMR spectrum is as follows:
δ＝1，1-2，4ppm（m）3H，δ＝4，15ppm（d????7Hz，tr????1.5Hz）2H，
δ＝7.35ppm（d????10Hz）1H，δ＝7.5ppm（d????7Hz）1H
Can make following compound with similar approach:
Figure 87106917_IMG55
R 1R 2R 3X Y n U V
H????H????H????F????F????2????Cl????F
H????H????H????Cl????Cl????1????Cl????F
H????H????H????Cl????Cl????2????Cl????F
Preparation 4-chloro-2-fluoro-5-(2,2-difluoro cyclo propyl methoxy) aniline
Make the 5g10% metal Pd of carrier with 36.9g 4-chloro-2-fluoro-5-(2,2-difluoro cyclo propyl methoxy by adding with gac under the normal temperature and pressure) oil of mirbane hydrogenation in 600ml ethanol.Leach catalyzer after hydrogenation is finished and steam solvent, obtain oily product 29.3g(theoretical value 89%), its NMR spectrum is as follows:
δ＝1，1-2，2ppm（m）3H，δ＝4，0ppm（d????10Hz????breit）2H，
δ＝5ppm（s????breit）2H，δ＝6.5ppm（d????7Hz）1H，
δ＝7.0ppm（d????10Hz）1H
Can make following compound with similar approach:
Figure 87106917_IMG56
R 1R 2R 3X Y n U V
H????H????H????F????F????2????Cl????F
H????H????H????Cl????Cl????1????Cl????F
H????H????H????Cl????Cl????2????Cl????F
Preparation 4-chloro-2-fluoro-5-(2,2-difluoro cyclo propyl methoxy) phenyl hydrazine
Get 29.3g 4-chloro-2-fluoro-5-(2,2-difluoro cyclo propyl methoxy) aniline, at first with 45ml half concentrated hydrochloric acid, handle with the 273ml concentrated hydrochloric acid then.Afterwards it is cooled to-10 ℃, the 17ml aqueous solution that is added dropwise to the 8.3g Sodium Nitrite is handled, and its interpolation speed should make the temperature of reaction mixture be unlikely and rise to more than-5 ℃.It in-5 ℃, is added dropwise to the 34ml concentrated hydrochloric acid solution of 57.3g tin chloride (II) dihydrate then after 3 hours in-15 ℃ of stirrings, its interpolation speed should make the temperature of reaction mixture be unlikely above-10 ℃.Room temperature heated overnight afterwards.It being cooled to 0 ℃ also slowly neutralizes to carry out aftertreatment with 430ml 32% caustic soda soln again.Filter to isolate the stannic hydroxide slurry that is settled out with Celite, and filter cake is with the ether washing and with mother liquor aqueous solution extracted with diethyl ether.Organic phase is combined the back with dried over mgso and except that desolvating.
Obtain oily product 26g(theoretical value 100%), its NMR spectrum is as follows:
δ＝1，1-2，3ppm（m）3H，δ＝4，0ppm（d????8Hz????breit）2H，
δ＝6，85ppm（d????7Hz）1H，δ＝7.0ppm（d????10Hz）1H
Can make following compound with similar approach:
R 1R 2R 3n X Y U V
H????H????H????2????F????F????Cl????F
H????H????H????1????Cl????Cl????Cl????F
H????H????H????2????Cl????Cl????Cl????F
Following embodiment shows the activity of The compounds of this invention.
Application examples A
In the greenhouse, the consumption of The compounds of this invention with 500 premium on currency emulsion/ha of 1kg active substance is sprayed on Matricaria and the Viola test plant before bud He behind the bud.Handle 3 weeks postevaluation result.The herbicidal effect of the standard evaluation preparation example 1-9 compound of eradicating fully with 0=non-activity and 4=.
Application examples B
With the consumption bud pre-treatment following plants of following compounds with 0.1kg active substance/ha, wherein compound evenly is sprayed on the plant with the form of 500 premium on currency emulsion/ha in the greenhouse.Estimate after handling for 3 weeks, with known substance by comparison, The compounds of this invention except that having significant weeding activity, also have very high selectivity.
Compd B r So Go Gl St Ab Ma Vi Av Al Ec Se Cy
No????4.1????4????4????0????0????4????4????4????4????4????4????4????4????4
Comparative formulation
EP61????741
No????1????2????3????1????1????3????3????4????4????2????2????2????4????1
EP105????721
No????1????3????4????2????1????3????4????4????4????2????3????4????4????0
Oxadiazole ketone 0300232402130
Judgement criteria
The 0=non-activity
The 1=slight damage
The medium damage of 2=
3=is badly damaged
4=eradicates fully
Plant name
Br＝Brassica????ssp.
So＝Solanumn????ssp.
Go＝Gossypium????hirsutum
Gl＝Glycine????max.
St＝Stellaria????media
Ab＝Abutilon????hybridum
Ma＝Matricaria????chamomilla
Vi＝Viola????tricolor
Av＝Avena????fatua
Al＝Alopecurus????myosuroides
Ec＝Echinochloa????crus-galli
Se＝Setaria????italica
Cy＝Cyperus????esculentus
Application examples C
With the consumption bud aftertreatment following plants of following compounds with 0.3kg active substance/ha, wherein compound evenly is sprayed on the plant with the form of 500 premium on currency emulsion/ha in the greenhouse.Estimate after handling for 3 weeks, with known substance by comparison, The compounds of this invention except that having significant weeding activity, also have very high selectivity.
Compd B r So Gl He St Ab Ma Vi Ch Ip Ze Tr Ho Or S rS e
No1.14????4????0????4????4????4????4????4????4????4????0????0????0????0????0????3
No3.14????4????0????4????2????2????4????3????4????3????0????0????0????0????0????4
No3.24????4????0????3????4????3????4????4????4????4????0????0????0????0????0????4
No3.42????3????0????3????1????1????2????3????3????2????0????0????0????0????0????1
No4.33????4????0????3????3????4????4????3????4????4????0????0????0????0????0????3
Comparative formulation
Oxadiazole ketone 4442233434222224
Judgement criteria
The 0=non-activity
The 1=slight damage
The medium damage of 2=
3=is badly damaged
4=eradicates fully
Plant name
Br＝Brassica????ssp.
So＝Solanumn????ssp.
Gl＝Glycine????max.
He＝Helianthus????annus
St＝Stellaria????media
Ab＝Abutilon????hybridum
Ma＝Matricaria????chamomilla
Vi＝Viola????tricolor
Ch＝Chrusanthemum????segetum
Ip＝Ipomoea????purpurea
Ze＝Aea????mays
Tr＝Triticum????aestivum
Ho＝Hordeum????vulgare
Or＝Oryza????sativa
Sr＝Sorghum????sativum
Se＝Setaria????italica
Application examples D
With the consumption bud aftertreatment following plants of following compounds with 0.3kg active substance/ha, wherein compound evenly is sprayed on the plant with the form of 500 premium on currency emulsion/ha in the greenhouse.Estimate after handling for 3 weeks, The compounds of this invention has very high weeding.
Compd E c Ce Cd Fi
No????1.1????1????1????2????3
No????1.2????4????2????4????4
No????3.2????4????1????3????4
No????4.3????3????1????3????4
No????4.4????4????3????4????4
No????5.1????1????1????3????3
No????6.1????4????4????4????4
Judgement criteria
The 0=non-activity
The 1=slight damage
The medium damage of 2=
3=is badly damaged
4=eradicates fully
Plant name
Ec＝Echinochloa????crus-galli
Cy＝Cyperus????esculentus
Cy＝Cyperus????difformis
Fi＝Fimbristylis????miliacea
Application examples E
Following table provides consumption and uses following compounds in the greenhouse, wherein compound is placed on (medication in the water) in the container that 1500 water are housed.Plant was handled in the 2-5 leaf phase.Medication 3 week postevaluation is to the damage effect of plant.
As shown in Table, The compounds of this invention has very high weeding activity to important rice weed.
Medication in the water
Compound ppm Ec Ce Cd Fi Sa El
No????3.2????10????4????1????3????3????-????-
No????4.3????10????4????1????4????4????-????-
No????4.4????1????4????3????4????4????-????-
3????4????3????4????4????-????-
No????5.1????1????4????2????2????2????-????-
3????4????4????3????4????-????-
No????6.1????1????4????4????4????4????-????-
3????4????4????4????4????-????-
No????7.1????3????4????-????4????-????3????4
No????8.1????3????4????-????4????-????3????4
No????9.1????3????4????-????4????-????3????4
Judgement criteria
The 0=non-activity
The 1=slight damage
The medium damage of 2=
3=is badly damaged
4=eradicates fully
-=not test (N.T.)
Plant name
Ee＝Echinochloa????crus-galli
Cy＝Cyperus????esculentus
Cy＝Cyperus????difformis
Fi＝Fimbristylis????miliacea
Sa＝Sagittaria????pusilla
El＝Eleocharis????acicularis

Claims (5)

1, formula I fontanel is for cyclopropyl compounds
Figure 87106917_IMG2
Wherein
R 1, R 2And R 3Be respectively hydrogen or 1-4 carbon alkyl,
X is hydrogen or fontanel element,
Y is the fontanel element,
N is 0,1,2 or 3
U and V be hydrogen or fontanel element and
W is following heterocyclic radical
Figure 87106917_IMG4
Wherein
T is the fontanel element, 1-4 carbon alkyl, 1-4 carbon fontanel substituted alkyl, CN or OR 9,
Q is CH or N,
Z is O or S,
R 4, R 5, R 6, R 7And R 8Be respectively straight chain, branching or ring-type 1-7 carbon alkyl also can be replaced by 1-6 fontanelle atom in case of necessity, or
R 4And R 5Also can form saturated together or unsaturation 4-7 annulus, wherein can contain heteroatomss such as O, S or N, in case of necessity also can by 1-3 methyl or 1-6 fontanelle atom replace and
R 9Be hydrogen, 1-4 carbon alkyl or 1-4 carbon fontanel substituted alkyl.
2, formula I fontanel is for the preparation method of cyclopropyl compounds
Figure 87106917_IMG5
Wherein
R 1, R 2And R 3Be respectively hydrogen or 1-4 carbon alkyl,
X is hydrogen or fontanel element,
Y is the fontanel element,
N is 0,1,2 or 3
U and V be hydrogen or fontanel element and
W is following heterocyclic radical
Figure 87106917_IMG6
Wherein
T is the fontanel element, 1-4 carbon alkyl, 1-4 carbon fontanel substituted alkyl, CN or OR 9,
Q is CH or N,
Z is O or S,
R 4, R 5, R 6, R 7And R 8Be respectively straight chain, branching or ring-type 1-7 carbon alkyl also can be replaced by 1-6 fontanelle atom in case of necessity, or
R 4And R 5Also can form saturated together or unsaturation 4-7 annulus, wherein can contain heteroatomss such as O, S or N, in case of necessity also can by 1-3 methyl or 1-6 fontanelle atom replace and
R 9Be hydrogen, 1-4 carbon alkyl or 1-4 carbon fontanel substituted alkyl,
It is characterized in that
A) with formula II fontanelle compound and the reaction of formula III phenol
R wherein 1, R 2, R 3X, Y and the definition of n cotype I, A is Cl, Br or L,
Figure 87106917_IMG8
U wherein, V and the definition of W cotype I,
Or
B) be 4,5,6 for making W, the formula I compound of 7-tetrahydrochysene indazole-2-base is with formula IV compound and the reaction of formula V compound
Figure 87106917_IMG9
R wherein 1, R 2, R 3X, Y, n, U, the definition of V cotype I,
Figure 87106917_IMG10
R wherein 10Be 1-4 carbon alkyl, 1-4 carbon fontanel substituted alkyl or 1-4 carbon alkoxyl group, and the formula I that can be alkyl in case of necessity with the T that makes like this is compound modified as reacting to such an extent that T is the corresponding compound of alkoxyl group or reacts to such an extent that T is that the corresponding compound of fontanel element and also available in case of necessity Na CN processing change into the corresponding compound that T is CN with phosphoryl chloride with the sulfuric acid dialkyl
Or
C) be 2H-1 for making W, 2, the formula I compound of 4-triazoline-3-ketone-2-base is with above-mentioned formula IV compound and the reaction of formula VI compound
R wherein 4And R 5The definition of cotype I, R 11Be 1-4 carbon alkyl,
Or
With above-mentioned IV compound of formula and the reaction of formula XII ketone acid
Figure 87106917_IMG12
R wherein 8The definition of cotype I,
Thereby make formula XI compound
Figure 87106917_IMG13
R wherein 1, R 2, R 3, R 8, X, Y, n, U and the definition of V cotype I are carried out the cyclisation processing and are made formula XX III compound with the phosphoric acid ester trinitride again
Figure 87106917_IMG14
R wherein 1, R 2, R 3, R 5, X, Y, n, U and the definition of V cotype I can also be reacted itself and formula X compound in case of necessity
R wherein 4The definition of cotype I, A is Cl Br or I,
Or
D) be 3H-1 for making W, 3, the formula I compound of 4-oxadiazole-2-ketone-3-base is with above-mentioned formula IV compound and the reaction of formula VIII acid derivative
Figure 87106917_IMG15
R wherein 6The definition of cotype I, R 12Be fontanel element or 1-4 carbon alkoxyl group, thereby make formula VII intermediate product
Figure 87106917_IMG16
R wherein 1, R 2, R 3, R 6, X, Y, n, the definition of U and V cotype I is with the derivatives reaction of reactive functionality with itself and phosgene or its again,
Or
E) be 2H for making W, 4H-1,2,4-triazine-3, the formula I compound of 5-diketone-2-base is with above-mentioned formula XII compound and the reaction of formula VII ketone acid
Figure 87106917_IMG17
R wherein 8The definition of cotype I,
Thereby make formula XI compound
Figure 87106917_IMG18
R wherein 1, R 2, R 3, R 8, X, Y, n, the definition of U and V cotype I, then with it with thionyl (two) chlorine or phosphoryl chloride and carrying out cyclisation and making formula IX compound with carbamate thereafter
Figure 87106917_IMG19
R wherein 1, R 2, R 3, R 8, X, Y, n, U and the definition of V cotype I are reacted itself and formula X compound again
R wherein 7The definition of cotype I, A is Cl, Br or I,
Or
F) be 4,5,6 for making W, 7-tetrahydrochysene-2H-1,2, the formula I compound of 3-triazolo [3,4-a] pyridine-8--3-olation-2-base is used the diacetyl oxide cyclisation with formula X V compound after with nitrous acid diazotization with piperidines-2-carboxylic acid reaction and thereafter
Figure 87106917_IMG20
R wherein 1, R 2, R 3, X, Y, n, U and the definition of V cotype I,
G) be 1,3,4,5,6 for making W, 7-six hydrogen-2H-isoindole-1, the formula I compound of 3-diketone-2-base is with above-mentioned formula X V and the reaction of formula X VI
Figure 87106917_IMG21
Wherein Z is O or S,
Or
H) be 2,3,5,6,7 for making W, 8-six hydrogen-1H-imidazo [1,5-a]-pyridine-1,3-diketone-2-base or 2,3,5,6,7,8-six hydrogen-1H-1,3,4-triazolo [1,2-a]-pyridazine-1, the formula I compound of 3-diketone-2-base is with above-mentioned formula X V compound and formula X VII or the reaction of X VIII compound
Figure 87106917_IMG22
Wherein Z is O or S, and Q is CH or N, R 15Be 1-4 carbon alkyl,
Or
Above-mentioned formula X V compound and phosgene or thiophosgene reaction can be made formula X IX compound,
Figure 87106917_IMG23
R wherein 1, R 2, R 3, X, Y, n, U, V and the definition of Z cotype I, and then with formula X IX compound and the reaction of formula XX compound
Figure 87106917_IMG24
Wherein Q is CH or N, and Z is O or S, R 15Be 1-4 carbon alkyl,
Or
I) formula XX I compound and formula XX II fontanel are reacted for methane Derivatives
Figure 87106917_IMG25
R wherein 1, R 2, R 3, U, V, W and the definition of n cotype I,
Figure 87106917_IMG26
Wherein X and Y cotype I the definition, B be hydrogen or
Figure 87106917_IMG27
OM, wherein M is a basic metal.
3, herbicidal formulations is characterized in that wherein containing the compound that at least a claim 1 compound or at least a claim 2 method make.
4, the herbicidal formulations of claim 3 is characterized in that wherein using with carrier and/or auxiliary agent.
5, application rights require 1 or the compound that makes of claim 2 method remove dicotyledonous and monocotyledons in the useful plant.
CN198787106917A 1986-10-14 1987-10-13 Novel halogenated cyclopropyl compound, its preparation method and as herbicide applications Pending CN87106917A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863635309 DE3635309A1 (en) 1986-10-14 1986-10-14 HALOGENCYCLOPROPYL COMPOUNDS, THEIR PRODUCTION AND USE AS A HERBICIDE AGENT
DEP3635309.4 1986-10-14

Publications (1)

Publication Number Publication Date
CN87106917A true CN87106917A (en) 1988-07-13

Family

ID=6311886

Family Applications (1)

Application Number Title Priority Date Filing Date
CN198787106917A Pending CN87106917A (en) 1986-10-14 1987-10-13 Novel halogenated cyclopropyl compound, its preparation method and as herbicide applications

Country Status (15)

Country Link
US (1) US4859230A (en)
EP (1) EP0268797A3 (en)
JP (1) JPS63218662A (en)
CN (1) CN87106917A (en)
AU (1) AU605183B2 (en)
BR (1) BR8705442A (en)
DD (1) DD279394A5 (en)
DE (1) DE3635309A1 (en)
DK (1) DK537587A (en)
FI (1) FI874514A (en)
HU (1) HU201068B (en)
IL (1) IL84138A0 (en)
PH (1) PH23048A (en)
SU (1) SU1618273A3 (en)
ZA (1) ZA877732B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4430287A1 (en) * 1994-08-26 1996-04-25 Basf Ag N-phenyltetrahydroindazoles, process for their preparation and their use as crop protection agents
CA2156652A1 (en) * 1994-08-31 1996-03-01 Minoru Takano Epoxyphenol derivatives and herbicides containing them as active ingredients
EP0729949A2 (en) * 1995-03-01 1996-09-04 Sumitomo Chemical Company, Limited 1,2,4-Triazol-3-ones as pesticides

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5890570A (en) * 1981-11-26 1983-05-30 Showa Denko Kk Oxadiazoline derivative and herbicide
PH18938A (en) * 1982-09-28 1985-11-11 Sumitomo Chemical Co 2-substituted phenyl-4,5,6,7-tetrahydro-2h-indazoles and their use
JPS59148785A (en) * 1983-02-15 1984-08-25 Sumitomo Chem Co Ltd Pyridotriazolium derivative, its preparation and herbicide containing the same as an active ingredient
JPS6113175A (en) * 1984-06-29 1986-01-21 Rhythm Watch Co Ltd Timepiece with touch switch
EP0259264A1 (en) * 1986-09-03 1988-03-09 Ciba-Geigy Ag 4-Methyl phthalimides
DE3731516A1 (en) * 1987-09-18 1989-03-30 Bayer Ag N-ARYL NITROGEN HETEROCYCLES

Also Published As

Publication number Publication date
DE3635309A1 (en) 1988-04-21
FI874514A (en) 1988-04-15
EP0268797A2 (en) 1988-06-01
HUT48241A (en) 1989-05-29
FI874514A0 (en) 1987-10-13
BR8705442A (en) 1988-05-24
HU201068B (en) 1990-09-28
IL84138A0 (en) 1988-03-31
ZA877732B (en) 1988-06-29
DD279394A5 (en) 1990-06-06
EP0268797A3 (en) 1989-03-29
SU1618273A3 (en) 1990-12-30
AU605183B2 (en) 1991-01-10
PH23048A (en) 1989-03-10
JPS63218662A (en) 1988-09-12
AU7937387A (en) 1988-04-21
DK537587D0 (en) 1987-10-14
DK537587A (en) 1988-04-15
US4859230A (en) 1989-08-22

Similar Documents

Publication Publication Date Title
CN1060478C (en) Substituted pyrazole derivatives
CN1025981C (en) Pyrimidine derivatives, processes for their production and herbicidal method and compositions
CN1073440A (en) The pyrazolyl-pyrazole of new replacement, its preparation method, and their intermediate and they are as the purposes of weedicide
CN1032479A (en) Replace azoles and its method for making of piperazine compounds and weeding purpose
CN1058490C (en) Tetrazolinone derivatives
CN1057837A (en) 2-benzo [C] furanone and heterocycle 2-benzo [C] furanone that replace
CN1046937C (en) Process for producing lignan compound
CN1058963C (en) Triazole derivative, insecticidal/acaricidal agent, and process for producing the same
CN1216534A (en) Novel heterocycle-substituted benzene derivatives and herbicides
CN1078721A (en) Pyridine carboxylic acid and herbicidal composition
CN86100928A (en) The herbicidal composition and the production method thereof that contain Pyridinylimidazoles alkane ketone compound
CN1107147A (en) Herbicidal substituted phenylaminosulphonylureas
CN86106281A (en) Semicarbazone class and thiosemicarbazone class
CN1294124C (en) Benzoxazole compound, process for producing the same and herbicide
CN1021824C (en) Substituted benzofurans herbicide active compound
CN1349532A (en) Substituted benzoylisoxazoles and the use thereof as herbicides
CN87100874A (en) The 5-amino-1-phenyl-pyrazoles
CN1110478A (en) Indazolesulfonylurea derivative, use thereof, and intermediate for production thereof
CN1282331A (en) Herbicides 3-(benzazol-4-yl) pyrimidine-dione-derivatives
CN1068822A (en) The benzothiazole derivant that replaces, its preparation and as herbicide applications
CN1078718A (en) The preparation method of sulphamide
CN1016661B (en) Herbicidal composition containing pyridinesulfonamide
CN87106917A (en) Novel halogenated cyclopropyl compound, its preparation method and as herbicide applications
CN87102275A (en) Selective herbicide and manufacturing thereof and use
CN1175255A (en) Hydantoin derivatives, process for producing the same and herbicides comprising the same as active ingredients

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication